EP1333976A1 - Procede de realisation de godets de trame dans une plaque d'heliogravure, et corps de base pouvant etre utilise dans ce procede - Google Patents
Procede de realisation de godets de trame dans une plaque d'heliogravure, et corps de base pouvant etre utilise dans ce procedeInfo
- Publication number
- EP1333976A1 EP1333976A1 EP01980111A EP01980111A EP1333976A1 EP 1333976 A1 EP1333976 A1 EP 1333976A1 EP 01980111 A EP01980111 A EP 01980111A EP 01980111 A EP01980111 A EP 01980111A EP 1333976 A1 EP1333976 A1 EP 1333976A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- support layer
- copper
- laser radiation
- base body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 24
- 239000000463 material Substances 0.000 claims abstract description 42
- 230000005855 radiation Effects 0.000 claims abstract description 33
- 238000002679 ablation Methods 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 35
- 229910052802 copper Inorganic materials 0.000 claims description 35
- 239000010949 copper Substances 0.000 claims description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 238000007646 gravure printing Methods 0.000 claims description 9
- 238000007639 printing Methods 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000004049 embossing Methods 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 230000003628 erosive effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000010894 electron beam technology Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010147 laser engraving Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000013070 direct material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41B—MACHINES OR ACCESSORIES FOR MAKING, SETTING, OR DISTRIBUTING TYPE; TYPE; PHOTOGRAPHIC OR PHOTOELECTRIC COMPOSING DEVICES
- B41B17/00—Photographic composing machines having fixed or movable character carriers and without means for composing lines prior to photography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/02—Engraving; Heads therefor
- B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
- B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/04—Printing plates or foils; Materials therefor metallic
- B41N1/06—Printing plates or foils; Materials therefor metallic for relief printing or intaglio printing
Definitions
- the invention relates to a method according to the preamble of patent claim 1 and a base body of a gravure printing plate according to the preamble of patent claim 8.
- DE-A 30 35 714 discloses a further method for producing pressure cups for an intaglio printing plate.
- the still "raw" gravure form was coated with an etchant-resistant varnish.
- the varnish was then removed with an electronic engraving device at the points where grid pits should later be available.
- a stylus, a laser beam or an electron beam was used as the electronic engraving device.
- an etching process was carried out to produce the grid cells.
- the manufacturing process described here was complicated and time consuming. A method analogous to this is described in DE-A 2 344 233.
- EP-B 0473 973 proposes to produce the cells no longer in copper but in zinc.
- the method described in EP-B 0 473 973 can be used, it is disadvantageous in the case of the gravure printing forms produced thereby that the entire gravure Printing technology is now geared towards copper as the material in which the grid cells are located.
- the object of the invention is to present a method and to create a base body in which or on the screen cup of a gravure printing form directly by means of laser radiation, preferably in copper, but also in other materials without an ejection crater rim, i.e. burr-free grid cups can be produced.
- the object is achieved in that a, preferably only a single ablation support layer is applied to the base body over the upper layer areas provided for the information embossing, through which scanning pits with the laser radiation by material ablation (evaporation and / or ejection of molten material) into the jacket areas are introduced and then this support layer is removed, whereupon burr-free rest cases are obtained.
- the laser radiation is radiation that is modulated in terms of its intensity over time. As a rule, pulsed radiation will be used, but this is not mandatory. Laser spikes, Q-switches, mode-locking etc. are also possible. When the support layer is removed, there is no change in the grid cells in the upper layer areas.
- the quality of the grid cells produced in this way without burr is so good that a hard layer, in particular a chrome layer, can be applied without aftertreatment.
- the chromium layer in gravure forms of this type is preferably applied with a layer thickness between 4 ⁇ m and 30 ⁇ m, in particular between 8 ⁇ m and 10 ⁇ m.
- the burr-free grid cells preferably in copper, can be achieved in particular by selecting the support layer in such a way that it enables good energy coupling for the laser radiation with good initiation of material ablation (ablation) to the underlying material with minimized directed radiation backscattering.
- Minimized radiation backscatter is important so that no radiation gets back into the laser resonator. This would be intensified there and could cause damage to the optical components.
- a good energy coupling of the laser radiation is important, since then only a small portion of the radiation remains, which is still necessary for a back reflection could come into question. On the other hand, a good energy coupling causes a strong heating of the material of the support layer.
- the support layer has changed to the liquid state, there is practically no longer any need to worry about radiation absorption. If one now selects this material of the support layer in such a way that the melting point of its essential material portion is low, the high radiation absorption also occurs quickly. However, the melting point should in any case be lower than that of the underlying upper layer material, in which the grid cells are then located. If the grid cells are to be in copper, the melting point should be below 1083 ° C.
- the metals would be silver with 961 ° C, aluminum with 660 ° C, gold with 1063 ° C (which, however, immediately falls out of the cost), gallium and germanium with 937 ° C, indium with 927 ° C, lead at 327 ° C, tin at 232 ° C, zinc at 419 ° C, etc.
- An essential material fraction of the layer material is understood to mean a percentage which causes the property mentioned above. Depending on the material, a substantial proportion of the material should be between 80% and close to 100%.
- the material of the support layer is said to be a material removal in which the
- the local thermal energy introduced with the laser radiation should cause the material underneath to melt as quickly as possible.
- this reproducible melting is only possible if the layer thickness of the ablation support layer is the same everywhere. If this is the case, the well volume to be generated can be precisely specified via the radiated maximum pulse intensity and the pulse shape. The easiest way to determine the well volume is by experiment. Good results have resulted in copper as information-bearing layer and zinc as erosion support layer with the layer thickness of between 1 micron to 15 microns, preferably microns between 5 and 10 microns is less than 10 with a layer thickness tolerance of "3, preferably better than 5 ⁇ 10 of" 5 , A zinc layer with such accuracy is best applied galvanically.
- the material of the ablation support layer should have the highest possible vapor pressure.
- "Background material” ejected by the laser pulse from the information-carrying layer, which still falls fluidly onto the support layer, causes it to melt and evaporate and is then thrown away by the steam with a further loss of heat.
- the vapor pressure of the "background material” should be at least five times lower than that of the material lying on it. If the example above remains, zinc has a vapor pressure that is about 100 times higher than that of copper.
- the material of the ablation support layer should be able to be removed well, in particular chemically, without attacking the information-carrying jacket regions.
- the wavelength of the laser radiation used is to be adapted to the absorption of the material of the ablation support layer.
- the wavelength must also be adapted to the dimensions of the grid cells to be produced in accordance with the optical imaging laws.
- a CO 2 laser (wavelength 10.6 ⁇ m) can be used for scanning cells with a diameter larger than 10 ⁇ m.
- an Nd: YAG laser (1.06 ⁇ m) is preferred.
- Pulse shaping and an optical structure for the beam guidance of the laser will preferably be carried out as described in EP 00 810 552.0. If an Nd: YAG laser is used, zinc has also proven itself in this case as the material of the ablation support layer.
- the ablation support layer not only initiates material removal in the underlying material, it also causes a switch-on delay for the drilling process in the underlying layer.
- the laser pulse has therefore already risen to a higher intensity value than its initial pulse value, which results in an increase in the drilling intensity. This results in a good, i.e. a hemispherical shape.
- FIG. 1 shows a cross section through the base body according to the invention in an enlarged view with a pulsed laser beam generating a scanning cell
- FIG. 2 shows a cross section analogous to FIG. 1, the removal support layer being removed here
- FIG. 3 shows a cross section analogous to FIGS. 1 and 2, a hard layer being applied here.
- Metallic rotogravure forms are usually made up of several functional elements.
- a steel cylinder is usually used as the base body 1.
- a copper layer 3 with a thickness of a few millimeters is applied to the steel cylinder.
- the copper layer 3 is the information-bearing gravure form.
- the information consists of an arrangement of a multiplicity of grid cells 5 which receive the color required for printing.
- a chromium coating 7 with a typical thickness of approximately 10 ⁇ m is applied as the top layer.
- the print information is now introduced directly into the copper layer 3 in its upper layer area 8 with a beam 9 of a pulsed Nd: YAG by material removal.
- the copper surface 11 is galvanically provided with a zinc layer 13 as a removal support layer with a small thickness tolerance (less than 5 ⁇ 10 "5 ).
- a small thickness tolerance less than 5 ⁇ 10 "5 .
- the laser pulse 9 for generating a grid 5 each pierces the zinc layer 13 while melting.
- Solid zinc has an absorption for the radiation 9 of the Nd: YAG laser of approximately 50%.
- solid zinc shows almost no directional reflection. Does the zinc go due to its relatively low melting and its low thermal conductivity compared to copper into the liquid state, there is almost 100 percent radiation absorption. There is a strong local heating of the zinc, which continues to pass it on to the underlying copper in the absorbing state, whereupon this also changes into the liquid state. Copper is now of an almost 100 percent reflection for the radiation 9 of the Nd: YAG laser (although the reflection does not come into effect because the copper is still covered by zinc) in the solid state, now liquid in an approximately 100 percent absorption passed.
- the copper material ejection or that of the zinc 15 lie on the zinc layer 13 and can be easily removed by chemically detaching it in a subsequent cleaning process.
- the exposed engraving (small cup 5) in copper 3 is burr-free and can be chrome-plated without any problems.
- Zinc in particular prevents the melts from sticking, reduces the initial reflection for the laser radiation 9 and therefore allows an efficient drilling process in copper 3.
- the method just described is of course not limited to zinc 13 as a copper coating. As stated at the beginning, a number of other materials are possible.
- the removal support layer to be applied to copper 3 does not necessarily have to be a metal layer either. Non-metals are also suitable, provided they have the required properties with regard to absorption, directed reflection and melting point.
- the base body 1 of a gravure printing plate does not necessarily have to be cylindrical; it can also be semi-cylindrical, flat or shaped differently.
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Or Reproduction Of Printing Formes (AREA)
- Printing Plates And Materials Therefor (AREA)
Abstract
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH221900 | 2000-11-15 | ||
| CH22192000 | 2000-11-15 | ||
| PCT/CH2001/000668 WO2002040272A1 (fr) | 2000-11-15 | 2001-11-15 | Procede de realisation de godets de trame dans une plaque d'heliogravure, et corps de base pouvant etre utilise dans ce procede |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1333976A1 true EP1333976A1 (fr) | 2003-08-13 |
| EP1333976B1 EP1333976B1 (fr) | 2006-08-23 |
Family
ID=4568057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01980111A Expired - Lifetime EP1333976B1 (fr) | 2000-11-15 | 2001-11-15 | Procede de realisation de godets de trame dans une plaque d'heliogravure, et corps de base pouvant etre utilise dans ce procede |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20040029048A1 (fr) |
| EP (1) | EP1333976B1 (fr) |
| JP (1) | JP2004512997A (fr) |
| DE (1) | DE50110828D1 (fr) |
| WO (1) | WO2002040272A1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8038731B2 (en) | 2006-03-24 | 2011-10-18 | L'oreal S.A. | Method of dyeing and lightening keratin materials in the presence of a reducing agent comprising a fluorescent disulphide dye |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060249491A1 (en) * | 1999-09-01 | 2006-11-09 | Hell Gravure Systems Gmbh | Laser radiation source |
| DE50304555D1 (de) * | 2002-10-17 | 2006-09-21 | Hell Gravure Systems Gmbh | Verfahren zur Herstellung einer Druckform für den Tiefdruck |
| AT504185B1 (de) * | 2003-07-03 | 2009-06-15 | Oebs Gmbh | Verfahren zur herstellung einer druckplatte |
| EP1985459A3 (fr) * | 2007-04-23 | 2009-07-29 | Mdc Max Daetwyler AG | Fabrication de formes d'impression à héliogravure |
| SE531975C2 (sv) * | 2007-04-23 | 2009-09-22 | Anders Bjurstedt | Anordning för tryckning i djuptryck |
| DE102008035203B4 (de) | 2008-07-28 | 2011-01-27 | Leibniz-Institut für Oberflächenmodifizierung e.V. | Verfahren zum Löschen und Neubebildern eines Druckzylinders |
| DE102009058845B4 (de) * | 2009-12-18 | 2012-12-06 | Christof Tielemann | Verfahren zur Herstellung einer Druckwalze mit einer Laser-gravierten Oberfläche |
| DE102012205702B3 (de) | 2012-04-05 | 2013-05-23 | Schaeffler Technologies AG & Co. KG | Verfahren zum Markieren von Bauteilen |
| JP6389695B2 (ja) * | 2014-08-18 | 2018-09-12 | 理想科学工業株式会社 | 感熱製版装置 |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE728837C (de) * | 1935-05-30 | 1942-12-04 | Josef Horn | Verfahren zum Herstellen von Flachdruckplatten |
| US2100258A (en) * | 1936-02-15 | 1937-11-23 | Reynolds Metals Co | Composite body of copper and aluminum or copper and magnesium, and method of making same |
| US3474457A (en) * | 1967-11-13 | 1969-10-21 | Precision Instr Co | Laser recording apparatus |
| US3539410A (en) * | 1967-11-20 | 1970-11-10 | Gen Photogrammetric Services L | Relief models |
| US3528965A (en) * | 1968-02-09 | 1970-09-15 | Beecham Group Ltd | Penicillin ester process and products |
| DE2218393A1 (de) | 1972-04-15 | 1973-10-25 | Steigerwald Strahltech | Mittels energiestrahls gravierbares werkstueck, insbesondere tiefdruckform oder dergleichen |
| DE2344233A1 (de) | 1972-09-09 | 1974-03-21 | Newton Horwood Ltd | Druckplatte und verfahren zu ihrer herstellung |
| US4060032A (en) * | 1975-05-21 | 1977-11-29 | Laser Graphic Systems Corporation | Substrate for composite printing and relief plate |
| US4357633A (en) * | 1979-07-11 | 1982-11-02 | Buechler Lester W | Engraving apparatus and method |
| US4328390A (en) * | 1979-09-17 | 1982-05-04 | The University Of Delaware | Thin film photovoltaic cell |
| JPS5646753A (en) | 1979-09-26 | 1981-04-28 | Dainippon Printing Co Ltd | Preparation of gravure lithographic plate |
| DE3047999A1 (de) * | 1980-12-19 | 1982-07-15 | Basf Ag, 6700 Ludwigshafen | Verfahren zur verringerung der abrasion von pigmenten und druckfarben und im abrasionsverhalten verbesserte pigmente und druckfarben |
| DK159251C (da) * | 1983-03-12 | 1991-02-18 | Basf Ag | Fremgangsmaade til lukning af spalten mellem en paa et dybtrykapparats trykformcylinder opspaendt dybtrykplades ender, samt indretning ved dybtryksapparatet, til udoevelse af fremgangsmaaden |
| EP0473973B1 (fr) | 1990-09-04 | 1995-11-29 | MDC Max Dätwyler Bleienbach AG | Procédé pour le traitement de plaques d'impression intaglio |
| DE4212582A1 (de) * | 1992-04-15 | 1993-10-21 | Hell Ag Linotype | Verfahren zur Gravur von Druckformen sowie Druckform zur Durchführung des Verfahrens |
| CH689917A5 (de) * | 1995-05-03 | 2000-01-31 | Daetwyler Ag | Verfahren und Vorrichtung zur Herstellung von Rasternäpfchen in der Oberfläche eines Tiefdruckzylinders. |
| JP3408923B2 (ja) | 1996-05-28 | 2003-05-19 | シャープ株式会社 | 画像表示装置 |
| US5807658A (en) * | 1996-08-20 | 1998-09-15 | Presstek, Inc. | Self-cleaning, abrasion-resistant, laser-imageable lithographic printing contructions |
| DE19840926B4 (de) * | 1998-09-08 | 2013-07-11 | Hell Gravure Systems Gmbh & Co. Kg | Anordnung zur Materialbearbeitung mittels Laserstrahlen und deren Verwendung |
| EP1072350A1 (fr) * | 1999-07-12 | 2001-01-31 | MDC Max Dätwyler AG Bleienbach | Procédé et dispositif pour effectuer une distribution de l'intensité dans rayon laser |
| DE10033629B4 (de) * | 2000-07-11 | 2011-12-01 | Tampoprint Ag | Druckklischee |
-
2001
- 2001-11-15 US US10/416,706 patent/US20040029048A1/en not_active Abandoned
- 2001-11-15 EP EP01980111A patent/EP1333976B1/fr not_active Expired - Lifetime
- 2001-11-15 JP JP2002542618A patent/JP2004512997A/ja active Pending
- 2001-11-15 WO PCT/CH2001/000668 patent/WO2002040272A1/fr not_active Ceased
- 2001-11-15 DE DE50110828T patent/DE50110828D1/de not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0240272A1 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8038731B2 (en) | 2006-03-24 | 2011-10-18 | L'oreal S.A. | Method of dyeing and lightening keratin materials in the presence of a reducing agent comprising a fluorescent disulphide dye |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040029048A1 (en) | 2004-02-12 |
| WO2002040272A1 (fr) | 2002-05-23 |
| DE50110828D1 (de) | 2006-10-05 |
| EP1333976B1 (fr) | 2006-08-23 |
| JP2004512997A (ja) | 2004-04-30 |
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